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Table of Contents
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Introduction Physical Properties of Sulphuric Acid Physical Data Table 1 General Physical Data for Different Concentrations Of Sulphuric Acid Table 2 Specific Gravity Correction Factor According to Temperature Table 3 Specific Gravity/Concentration Chart for Sulphuric Acid Graph 1 Freezing Point Curve for Sulphuric Acid and Oleum Graph 2 Viscosity of Sulphuric Acid at Various Temperatures Graph 3 Specific Heat of the Sulphuric Acid Water System Bulk Storage of Sulphuric Acid Storage Tanks Piping, Valves, Fittings and Gaskets Unloading Facilities Air Supply Tank Truck Unloading Responsibilities Customer Responsibilities Truck Driver Responsibilities General Trailer Unloading Procedures Safety Precautions Unloading Steps Containment and Clean-up Procedures for Sulphuric Acid Personal Protective Equipment Containment of Spills Neutralization Disposal of Waste Transfer Procedures Materials of Construction Containers and Fittings
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Table 4 Sulphuric Acid Transportation Information How to Request Emergency Response for Chemical Emergencies Involving Sulco Products Information Required by Sulco to Provide Assistance for Chemical Emergencies Sulco Chemicals Limited Contact Information
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Introduction
The production of sulphuric acid, or Oil of Vitriol, began in the Middle Ages, where it was obtained in small quantities in glass vessels in which sulphur was burned with saltpeter in a moist atmosphere. Larger rates of production became possible with the introduction of lead chambers as reaction vessels by Roebuck, in Birmingham, England in 1746. Sulphuric acid is the product of sulphur trioxide gas reacting with water. SO3 (g) + H20 (l) ! H2SO4 (l) Important uses of sulphuric acid includes fertilizer production, petroleum refining, pigment production, steel pickling, non-ferrous metals extractions and in the manufacture of explosives, detergents, plastics and man-made fibers, waste water treatment, and steam production (regeneration of weak acid cation exchange resins). It is the objective of Sulco Chemicals Limited to maintain a high quality standard in the chemical industry. Meeting the service and product quality demands of our customers are the primary factors in determining our success. As a Responsible Care! member of the Canadian Chemicals Producers Association, Sulco Chemicals Limited is committed to taking every practical precaution towards ensuring that its products and operations do not present an unacceptable level of risk to its employees, customers, the public or the environment. Sulco is registered under ISO 9002, ISO 14001, and ANSI/NSF 60 International Standards. The purpose of this bulletin is to aid our customers in handling, transporting and storing sulphuric acid. If further information is required, contact Sulco Chemicals Limited at (519) 669-1332 for assistance.
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For temperatures above 15.6C add the correction. 15.6C subtract the correction.
Table 3
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Graph 1
sulphuric acid
oleum
Wt. % H2SO4
Graph 2
+"#,#-
Viscosity in Centipoise
!"!-
#",""$#,##%$,$$&%,%%'&,&'*),)*-
Wt. % H2S04
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Graph 3
! ") ! ! !
! "( ! ! !
! "' ! ! !
! "& ! ! !
! "% ! ! !
! "$ ! ! !
! "# ! ! !
Wt. % H2S04
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The normal practice is to size the storage tank to have 1! times the capacity of the tank trailer to be received. Storage tank and delivery load size is also dependent on the customer usage rate and minimum inventory levels. Maximum Trailer Size 40,000 kg Tank Size 60,000 kg
This tank size (60,000 kg) corresponds to approximately 33,000 litre or 7,200 IGal. It is recommended that the maximum tank level be 90% for non-fuming acids and 85% for fuming acids. Both horizontal and vertical style tanks are used for sulphuric acid storage. A 1/8 corrosion allowance should be added to the design thickness of carbon steel tanks. 2. Materials of Construction
Storage tanks for unpressurized 93% sulphuric acid and most grades of oleum are normally constructed of carbon steel. The corrosion of carbon steel by sulphuric acid, results in the evolution of hydrogen, and the formation of iron sulphate, which will normally settle to the bottom of the tank. Depending on several factors, including temperature and the residence time of the acid in the tank, the iron content of electrolytic grade sulphuric acid may increase to beyond acceptable limits. To prevent this, storage tanks may be lined with a phenolic resin such as Heresite or anodically protected. 316-stainless steel may also be used to avoid iron contamination, however elevated levels of chrome and nickel may be experienced when acid is stored for prolonged periods of time. 3. Tank Location
Storage tanks should be located such that tank trailers have free accessibility within 10 feet of the tank loading nozzle. If possible, tanks should be elevated to take advantage of gravity feed to process since an acid pump will add to both the
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overall initial cost of storage facilities as well as increased maintenance costs. Avoid catch basins and storm sewers in the truck unloading area.
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4.
Storage tanks should be supported by reinforced concrete footings. It is also recommended that storage tanks should be surrounded by a dike, which is 125% times the capacity of the tanks. Dike material should be of concrete or earth lined with compacted clay or a synthetic liner such as Dunseal Hypalon. Both the local branch of the Ministry of the Environment and the Municipality concerned should be consulted for more specific guidelines regarding installation and diking. 5. Tank Fittings
All storage tanks should be equipped with the following: A 2 schedule 80 carbon steel or schedule 40, 316-stainless steel, 150 lb flanged end-loading line brought down to waist level for easy accessibility. Depending upon the piping arrangement, it may be desirable to equip this line with a flanged plug valve adjacent to the main hook up flange to allow rapid shut off and containment of the acid in the line in the event of the tank being over filled. A minimum 2 schedule 80 vent/overflow line piped down to ground level and away from the loading line within the dike. PVC may also be used as this will avoid corrosion deposits on the carbon steel pipe which may choke the vent off over time. A 24 manway with a 2 schedule 80 secondary outlet equipped with a blind flange to allow dipping of the tank. Installation of a level indicating system with a high level alarm is recommended. A 2 schedule 80 flanged bottom outlet with a 4 standpipe (for horizontal tanks) inside the tank to prevent any accumulated iron sulphate from carrying over to process. This outlet should be equipped with a quarter turn plug valve as well as an emergency shut off plunger type valve (for large tanks). The plug valve should be located as close as possible to the tank outlet nozzle. A 2 schedule 80 outlet with no standpipe, to allow for periodic draining of the tank. This outlet should be equipped with a plug valve and a blind flange.
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Piping to the process should be of schedule 80 carbon steel, or schedule 40, 316-stainless steel with slip on welded flanges. Piping should be sized for an acid velocity of 3.5 feet/second or lower to minimize the erosive effects of the acid. Care should be taken at both the design and operation stages to avoid liquid full sections of pipe between closed valves since the hydrogen produced by steel corrosion can cause dangerous pressures especially in warmer weather. Quarter turn plug valves have been found to give good service with sulphuric acid. The recommended type should have a flanged end ductile iron body with an alloy 20 plug or Teflon encapsulated plug and a Teflon lining. Gasket material should be Teflon. Unloading Facilities Air Supply It is recommended that a compressed air supply be made available at the unloading area. All of Sulco Chemicals Limited tank trailers are equipped with eduction pipes for unloading by pressurizing the tank trailer. The recommended pressure at the trailer is 30 psi but must be less than 35 psi. The air supply should be equipped with a shut off valve, a pressure reducing valve, a pressure gauge, a safety relief valve (set at a maximum of 40 psi), a quick opening manual relief valve, and 50 feet of 1 flexible air hose. The air supply valves should be freely accessible and located away from the storage tank and associated acid piping. Trucks equipped with air compressors are available on request.
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6. The customer must make sure that the facility for unloading is designed to minimize the seriousness of any accident. Particular attention should be paid to the location of the overflow vent. If the tank is overfilled then the overflow vent should direct the liquid away from buildings, isolation valves and air shutoff valves and into the dike. Also, in the case of a ruptured unloading hose the air shutoff valve and liquid isolation valves should be far enough removed from the loading area so that the leak can be stopped quickly and safely. Truck Driver Responsibilities 1. The truck driver must make sure that all equipment on his truck, including unloading hoses, is in good order. He must carry a set of protective clothing including safety goggles, rain suit, face shield, gloves, boots and any other equipment as required by the customer. 2. The truck driver is responsible for all connections made at the truck. He/she will assist with connections to the customers equipment but only at the customers request and under their supervision. It is important that both the customer and the truck driver be suitably trained so that they know the proper action to be taken in the case of a spill and what medical treatment would be necessary in the case of injuries. This information is provided with the objective to prevent accidents. Should further assistance be required, please contact Sulco Chemicals Limited at (519) 669-1332.
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Unloading Steps 1. 2. Instruct the driver where the trailer is to be parked for unloading. Obtain the bill of lading and necessary quality documents from the driver (Certificate of Analysis, samples, weight ticket etc.). Verify the product is correct. Verify the amount of material on the trailer and confirm storage tank availability. Sign the bill of lading if all is correct to acknowledge acceptance. The unloading hose must be hooked up from the trailer to the unloading connection before any valves are opened. Note the location of any emergency shutoff valves equipped with the trailer.
3.
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4.
Open the main valve on the trailer and any valves to the storage tank. This allows the acid to begin flowing as soon as enough pressure is available in the trailer. Connect the regulated air supply line (Maximum 35 psi) to the trailer and open all valves leading from the air compressor to the tank truck with the last valve opened at the tank truck. Confirm air pressure < 35 psi before opening last valve at the tank truck. The acid will begin to flow as the pressure builds up in the trailer. The acid will continue to flow until the entire truckload is off loaded. The hose will jump and the sound of air rushing through will be evident when the trailer is empty. During the unloading period, the tank level must be continuously monitored. Shut off the air supply at the trailer first and all the way back to the air compressor. Disconnect the air supply line from the trailer. The main unloading valve on the trailer can be left partially open to blow any product free of the line for one minute. The trailer can be vented slowly through the air supply valve to atmosphere.
5.
6.
7. 8. 9.
10. Close the main valve on the trailer unloading line followed in succession by the valves leading to the storage tank. 11. The drain valve on the unloading line can be opened to drain any product from the unloading line. Once the line is confirmed to be free of product and any pressure, the unloading hose can then be disconnected at the trailer and the tank connection. Alternatively, permanent truck unloading hoses can just be flanged and loaded back on the trailer. 12. Remove wheel chocks and warning signs before moving trailer.
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Neutralization a. Caustic Soda 1 tonne of 93% acid requires 1.5 tonnes of 50% caustic soda. The most effective reagent for neutralizing large pools of acid is caustic soda solution, which is normally shipped in 50% strength solution. If freezes at approximately 13C. However, 50% caustic soda should never be added to strong sulphuric acid as it reacts violently and considerable spray results. The acid should first be diluted with water from a safe distance using a fire hose with sufficient force that the water goes down in the acid. Once the initial dilution to 50% or less has been accomplished, 50% caustic soda and water from the hose can be run down in to the acid together. It would of course be more effective to add the water through a length of submerged steel pipe to get better mixing but this may be difficult to arrange. During dilution and neutralization, the height of the retaining dam needs to be sufficient to contain the liquid. b. Soda Ash 1 tonne of 93% acid requires 1 tonne of soda ash. Dry soda ash is an effective reagent for neutralizing small spills and areas of soil, which have been wetted with acid, but it is not too effective with deep pools of acid. It is ideal for finishing off the neutralization of acid, which has been diluted and partially neutralized with caustic soda. There is less risk of ending up with a strongly alkaline solution, since as the end-point is reached the foaming reaction which accompanies soda ash addition will cease. c. Lime Quicklime and slaked lime are often more readily available than caustic soda or soda ash. However, they are difficult to use, and the formation if insoluble calcium sulphate results in poor utilization of the lime and a messy area to clean up later. Lime is an effective diking material for acid if earth is not available. d. Limestone Crushed limestone (1/4 to !) is excellent for constructing dams and for neutralizing and stabilizing the soil once the acid has been diluted, neutralized and discharged. Limestone spread over the area is harmless to animals and humans (the other alkalies are not), and with subsequent soil cover, vegetation can be restored.
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Disposal of Waste The pH of the effluent liquid should be in the range of 6.0 to 9.0 and must meet local regulations before being sent for disposal. Transfer Procedures The method selected for transferring acid from derailed tank cars or damaged road trucks to other containers will depend on the condition of the tank, its orientation, and the accessibility of the tank fittings. Acid tanks are normally unloaded either by pumping or by the application of air pressure. If for some reason neither of these is possible, the use of a vacuum truck to remove the acid to a disposal area should be considered. With sulphuric acid the maximum suction lift is seventeen feet. There may be occasions when it is desired to pick up spilled acid from pools in the ground. That should not be attempted if the acid has been diluted by surface water to a strength of less than 70%, since below that level acid reacts rapidly with mild steel. Acid strength can be judged by a hydrometer if one is available. (A density of 1.6 or greater indicates a strength above 70%.) Materials of Construction Strong sulphuric acid (over 70%) is normally handled in carbon steel piping and tanks. For components subject to wear such as pumps and valves, 316 stainless steel and alloy 20 are used for prolonged life. Copper and brass fittings must be avoided. Flexible pipe connections are preferable by using a length of PTFE lined hose. For gaskets, PTFE should be used.
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Containers and Fittings a. Tank Trucks Tank trucks in acid service are variable in size and fittings. They will made of 316 stainless steel, up to 40 tonne capacity and equipped with valves for bottom unloading or for top loading through an eduction pipe using air pressure or pump. b. Small Containers Sulphuric acid is packaged in 35 kg carboys, 350 kg drums and 1425 kg totes.
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Table 4
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How to Request Emergency Response for Chemical Emergencies Involving Sulco Products
1. 2. Gather information that will be needed by Sulco, as described on the following page. Call the following 24-hour Emergency Number:
(519) 669-5166
3. When your call goes through, state that you have a chemical emergency involving a Sulco product, and that you need assistance. Provide the information requested, and ask for the aid you require. A qualified person will return your call to provide assistance. If you have not received a return call within 20 minutes, call back (519) 669-5166. When your call is returned, you may be asked for additional information. Provide as much as you can without delay or guessing. Note: For chemical emergencies involving products not supplied by Sulco, contact the supplier. If you dont have the number, or if you need immediate advice, call the following number: For emergencies in Canada: Call collect to CANUTEC (613) 996-6666
4. 5.
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http://www.ccc-group.com/sulphur
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